Non PFOS & Non PFOA TARC Introduction AZ AQUATAR-VIII VIII-Series ~ for i-line, i KrF, and ArF application ~ November, 2007 AZ Electronic Materials (Japan) K.K. Shizuoka Technology Center R&D-1
1. General Introduction on AZ AQUATAR Family Providing TARC products as advanced implant or C/H solution to many customers in the world(80% of Market share) The 1 st to commercialize PFOX & Telomer free TARC, AZ AQ-8A in the market (the safest material in EHS aspect) Long production history of AQ-8 for 3 years in the market AZ AQ-8B was developed for N type of KrF resist AZ TARCs Refractive Index Materials Applications 365nm 248nm 193nm AZ AQUATAR 1.44 1.48 1.56 PFOA i-line AZ AQUATAR-IIIS 1.42 1.44 1.49 PFOS KrF&ArF AZ AQUATAR-VI-A 1.40 1.43 1.45 PFOS KrF&ArF AZ AQUATAR-VII 1.40 1.43 1.50 PFOA KrF&ArF AZ AQUATAR-VIII-A 1.41 1.45 1.52 Non PFOS Non PFOA All AZ AQUATAR-VIII-B 1.43 1.46 1.55 Non PFOS Non PFOA i-line&krf 2
1. AZ TARC Technology Road Map 365nm Novolak 248nm CA resist 193nm CA resist AQUATAR (1.44/1.48/1.56) PFOA AQUATAR-7 (1.40/1.43/1.45) AQUATAR-3S (1.42/1.44/1.49) PFOS AQUATAR-6 (1.40/1.43/1.45) Fluoro Polymer AQUATAR-8A (1.41/1.45/1.52) AQUATAR-8B for KrF N resist (1.43/1.46/1.55) 3
AZ AQUATAR-8 Series PFOX & Telomer Free Chemistry Fluorinated main chain unit linker group fluorinated pendant unit ( C 4 ) solubilizing group Fluoropolymer platform It is expected that acute bio effect is weak Non telomer pendant platform No biodegradation feature has been confirmed and low risk to release low molecular weight perfluoro substances Low bioaccumulation feature Length of the polymer pendant group is less than 4, so it does not yield any PBT compounds upon ultimate biodegradation PFOS C 8 Telomer 9F 3 C CF 2 CF 2 CF 2 SO 3 OH CF CF2 CF2 CF2 2 F PFOA 3 C CF 2 CF 2 CF 2 CH 2 CH 2 OH CF CF2 CF2 CF 1 2 2 F 3 C CF 2 CF 2 CF 2 CF2 CF2 COOH 4 CF 2 5
Optical Parameter Index of Refraction n Extinction Coefficient k 1.65 1.60 1.55 AQ-8A AQ-8B Telomer TARC i-line KrF ArF 0.30 0.25 0.20 AQ-8A AQ-8B Telomer TARC i-line KrF ArF N 1.50 K 0.15 1.45 0.10 1.40 0.05 1.35 150 250 350 450 550 650 750 wavelength(nm) 0.00 150 250 350 450 550 650 750 wavelength(nm) sample cauchy coefficient optical parameter A B(um 2 ) C(um 4 ) N@193nm K@193nm N@248nm K@248nm N@365nm K@365nm N@633nm AQ-8A 1.3914 0.0046 0.0000 1.52 0.00 1.44 0.00 1.42 0.01 1.40 AQ-8B 1.4040 0.0051 0.0000 1.55 0.01 1.46 0.00 1.43 0.01 1.42 Telomer TARC 1.4093 0.0563 0.0000 1.58 0.02 1.50 0.00 1.47 0.01 1.44 Coating condition Track : TEL Mark 8 Substrate : bare-si, w/o adhesion Bake : 90 o C/60sec FT : 40nm Measurement condition Ellipsometer : J.A.WOOLLAM VUV-VASE 5
2.4 Resist swing reduction effect in 365nm application Substrate : Silicon with HMDS(90C/60s) Resist : MiR703, Variable FT, 90C/60s PAB, 110C/60s PEB TARC : 64nm FT, NO PAB Exposure : Nikon NSR1755i7B NA=0.54, Conv. Develop : AZ 300MIF(2.38%), puddle 60s Mask pattern : 450nm L/S(1:1), binary 600 W/O TARC Swing Reduction Ratio CD(nm) 550 500 450 400 AQ AQ-8A AQ-8B AZ AQ 45 : 62% AZ AQ-8A 45 : 83% AZ AQ-8B 45 : 79% 350 300 250 900 950 1000 1050 1100 Resist Film Thickness(nm) Swing Reduction Ratio = 1 (A TARC / A w/o TARC ) 6
2.5 Resist swing reduction effect in 248nm application Substrate : BARC(90nm FT,180C60s PAB) Resist : DX7260P, Variable FT, 120C/60s PAB, 130C/60s PEB TARC : 43nm FT, 90C/60s PAB Exposure : Canon FPA-3000 EX-5, 0.63NA, 1/2Ann. Develop : AZ 300MIF(2.38%), puddle 60s Mask pattern : 200nm L/S(1:1), binary 250 225 w/o TARC AQ-8A AQ-8B Swing Reduction Ratio AZ AQ-8A 45 : 83% AZ AQ-8B 45 : 79% CD(nm) 200 175 150 200 250 300 350 400 Resist Film Thickness(nm) Swing Reduction Ratio = 1 (A TARC / A w/o TARC ) 7
2.6 Resist swing reduction effect in 193nm application Substrate : Silicon with HMDS(90C/60s) Resist : AX1120P, Variable FT, 120C/90s PAB, 120C/90s PEB TARC : 32nm FT, 90C/60s PAB Exposure : Nikon NSR S306C, NA=0.78, 2/3Ann. Develop : AZ 300MIF(2.38%), puddle 30s Mask pattern : 120nm L/S(1:1.5), binary 250 200 W/O TARC AQ-8 Swing Reduction Ratio AZ AQ-8A 25 : 70% CD(nm) 150 100 50 160 185 210 235 260 Resist Film Thickness(nm) Swing Reduction Ratio = 1 (A TARC / A w/o TARC ) 8
6. Summary table of AZ AQUATAR Family Products wafer AZ AQUATAR 8" i-line AZ AQUATAR 45 12" AZ AQUATAR-IIIS 45 8" KrF AZ AQUATAR-IIIS 33 12" AZ AQUATAR-VI-A-30 8" ArF AZ AQUATAR-VI-A 25 12" AZ AQUATAR-VII-45 8" KrF AZ AQUATAR-VII-A 30 12" 12" i-line AZ AQUATAR-VIII-A 45 AZ AQUATAR-VIII-A 30 12" KrF AZ AQUATAR-VIII-A 25 12" ArF N value(k=0) *ideal N value( N resist ) 633nm 365nm 248nm 193nm - 1.33 1.33 1.30 1.41 1.42 1.44 *Each ideal N was caluculated by using N i-line&krf resist =1.77, N ArF resist =1.70 **Minimal dispense volume was determined by visual inspection for 12 inch wafer. 1.38 1.39 1.40 1.43 1.40 1.43 1.40 1.41 1.45 1.52 65 Optimal FT(nm) λ/4n 365nm 248nm 193nm 1.42 1.44 1.48 1.56 64 43 31 1.49 65 43 32 **Mini.Dispense V(mL) 8 inch 12 inch 1.0 43 32 2.5 on Resist PH 3.0 3.3 2.5 5.0 2.2 1.45 65 43 33 2.0 4.5 1.50 65 43 32 1.0 3.0 5.0 1.8 Chemical PFOA PFOS 2.9 PFOS 3.4 PFOA F-polymer 9
AZ AQUATAR-8 series Process Recommendation 1. Process recommendation : CBC process 2. Filter recommendation : PE filter with wet treatment or pore size<0.05um Smaller pore size is BETTER for micro bubble, but need to adjust pump & dispense condition carefully. 3. Coating method : Static Dispense 4. Coater recommendation : Dedicated coater DON T SHARE with RELACS 5. EBR recommendation : DI water 10
Summary of PFOX & Telomer FREE TARC AZ AQUATAR-8 Series only universal PFOX & Telomer FREE TARC product in the market the safest TARC in EHS aspect >80% of market share in PFOS FREE TARC Stable Supplibility for 3 years Long Production History in many customers for >2 years Broad Resist Compatibility in 365 193nm Preferable Swing Control in 365 193nm Long Shelf Life 1 YEAR at 5 25C Less Defectivity from customer feedback 3 Grades of AQ-8, 25, 30, 45 fully can cover customer s need AQ-8B was developed for N -type of KrF resist 11
APPENDIX 12
Ap-1. Optical theory t Air (n=1) A B TARC Resist Substrate Required refractive index to be equalized light intensity in A and B n TARC = (n air n resist ) 1/2 n : Refractive index Required thickness to be shifted optical phase at 1/2π in A and B t =λ / 4n TARC t : Film thickness of TARC λ: Wavelength 13
Ap-2. Material Information of AZ AQUATAR-VIII-A Film Thickness(nm) 100 AQUATAR-VIII-A 25 AQUATAR-VIII-A 30 90 AQUATAR-VIII-A 45 80 365nm 248nm 70 193nm 60 50 40 30 20 10 500 1000 1500 2000 2500 3000 3500 4000 4500 Spin Speed(rpm) Cauchy Parameter Unit um nm A A 1.384 1.384 1.384 B 5.035E-03 5.035E+03 5.035E+05 C 0.000E+00 0.000E+00 0.000E+00 1.40 N 633nm 365nm 248nm 193nm N 1.42 1.45 1.52 K 0.01 0.00 0.00 Optimal FT(nm) 64 43 32 N 633nm value is caluculated from A, B,C values N 365nm,258nm,193nm values are actual values measured by Ellipsometer Optimal FT(nm) = λ/4n 14
Ap-3. AZ AQUATAR series install guide Water based TARC is promising to provide a lot of benefits in the customer s process, but the customers need to pay close attention to the TARC install to make a good line condition without micro bubble issue. This install guide is agreed to by TEL. a) TARC coater Use a dedicated TARC coater system by a coater supplier (TEL, etc.). b) Dummy dispense Keep the nozzle tip and line clean by periodical dummy dispense. c) Suck back Optimize the suck back condition. EX.) Adjust the liquid breaking position to 0.5mm upper from the tip of nozzle, and then the final position after the suck back to 2-3mm upper for 2-3 sec. Refer to a TARC coater operation guidance by your track maker on further detailed suck back adjustment. Suck back adjustment is one of KEY factors to achieve micro bubble free. 2-3mm 0.5mm Suck back 15
Ap-3. AZ AQUATAR series install guide d) Filter Use PE filter. PE filter requires hydrophilic treatment before the install (1 gallon of IPA flushing). Nylon filter is NOT suitable for some AQUATAR series with low ph(<2.0). It is the most important to make a good filter condition. e) Plumb in a virgin line (see SOP-1) f) Tubing From hydrodynamics view, use the same size of PFA tube and minimize the connection number in the line. Check if tube twist & bending, and some bubbles occur in the line visually. g) Dispense rate Adjust to preferable dispense rate( <1 ml/sec) h) EBR / BSR Use DI water or a hydrophilic solvent(ebr7030, PGME, etc.). Especially pay attention to rebounding back to a wafer choosing DI water as EBR/BSR. 16
Ap-3. AZ AQUATAR series install guide(sop-1) e) Plumb in a virgin line 1. Leave 2 bottles of AQUATAR in CR chemical box for 1 day 2. Purge the line with 1 gallon of IPA (electronic grade) 3. Fill IPA in the line for 1-2 days 4. Empty the line 5. Install the filter In PE filter case, purge 1 gallon of IPA with PE filter for hydrophilic treatment. 6. Check the line defectivity by a defect measurement tool (surface scanner etc.) Inspect the wafer after IPA coating & spin dry 7. Purge the line with > 3 gallons of clean DI water 8. Install the TARC 9. Purge the line with 1 gallon of the TARC After filling the TARC in the line and vent bubbles in the filter perfectly, take off N 2 pressure from the bottle, periodical vent from the filter would be effective to make a good line condition. 10. Install a new bottle of TARC 11. Check the line & filter carefully again after 1L of purge, and then setup your dispense. Check the line cleanness carefully replacing from a resist or BARC line, EX.) Purge > 1 gallons of thinner with strong solubility (NMP, etc.), and then fill it in the system for a week prior to the SOP-1. 17
Ap-4. Filter information on AQUATAR-VIII-A by Entegris Dispense Frequency vs. LPC value for each filter by Entegris 10000 LPC:KL-27(RION) >0.1um Particle counter Syringe sampler 16 Sampling vessel Counts/mL @KL-27 1000 100 10 0.01um-UPE 0.02um-UPE 0.05um-UPE IG3 Valve 1 0.02um-PCM 0 10 20 30 40 50 60 70 80 90 100 Test filter dispense frequency(n) Dispense condition: 1mL/sec 7sec 700mL 18
Ap-5. AZ AQUATAR-VIII-A shaking test Shake the samples for 30s initial 1H 3H 12H AQ-8A AQ-3 19
Ap-7. Material Compatibility-2 AZ TARCs can mix with Hydrophilic solvents (PGME, EBR7030, EL, NMP,etc. ). AZ TARCs can NOT mix with Hydrophobic solvents (PGMEA,EEP, etc.) Recommend to separate TARC coater cup & drain tank from organic materials (BARC, resist, etc.). 20
Ap-7. Material Compatibility-1 PFOS TARC PFOA TARC AQUATAR-VIII-A TARC R200 R500 R602/S680 TARC: AZ AQUATAR, AQUATAR-III, III-S, VI, VII, VIII-A PFOS TARC: AZ AQUATAR-III, III-S PFOA TARC: AZ AQUATAR, AQUATAR-VII TARC/TARC combination can mix freely. TARC/RELACS combination can NOT mix basically, except TRAC/R200 & PFOA TRARC/R500 combinations. Recommend to separate TARC coater cup & drain tank from RELACS s 21